Bluish-green vat dyes and process of making them.



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' cene-L9-dioarboxylic acid imid with caustic cnanr. nos, orcnaianorrmvn, r ON-THE-RHINE, GERMANY, assrenons 'rc nrscrunwresnarnn-on-rnn, cane 1r nnursn-cnnnn var nrns AND Ito Drawing. e.

To all whom it may concern:

Be it known that we, MICHAEL es and PAUL NAWIASKY, citizens of theAustrian Empire, residing at Charlottenburg andLudwigshafen-on-the-Rhine, Germany, have invented new and usefulImprovements in Bluish-Green Vat Dyes and Processes of Making Them, ofwhich the following is a specification.

The specification of application Serial No. 776,541 (Patent No.1,216,134) describes and claims generically a new class of vat coloringmatters, which are characterized by being soluble in alkalinehydro-sulfite solution giving red solutions and which dye cotton greenshades of excellent lastness. The said application also claims a genericprocess of producing such dyes by subjecting an aceanthrene-quinone-oximbody to the action of a caustic alkaline melt. The said applicationfurther claims the specific coloring matter obtainable by meltinganthraalkali, and states that this specific coloring matter yields acherry-red vat and dyes cotton a beautiful full green. This specific dyeapparently possesses anv unsubstituted group.

In the present application we desire to claim speclfically a class ofcoloring matters which falls generically under the generic claims of thesaid application-Serial No. 77 6,541, but which are not specificallymentioned or claimed therein.

Our new .class of coloring matters are characterized by possessing asubstituted 1mid group lily giving from red to violet vats with al allnehydrosulfite solutions and by yielding bluish-green shades on cotton, tat is to say, they yield more chluish shades of green than does thecoloring a ter obtainable from anthracene-1.9-dicarboxylic acid imid andclaimed ecifically in No.- 7 ,5dl,

the said application ":1:

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in which the hydro en of the imid group has been substitute forinstance, hy-

droxyl, or alkyl, or .aryl. 0r we can take a coloring matier obtainablefrom an anthracene-L9-dicarboxylic acid imid body in which the hydrogenatom of the imid group has not been substituted, and then treat thecoloring matter in such a'rnanner as to efi'ect the introduction of asubstituent into the imid group, or groups. This can beefl ected, forinstance, by treating the said non-substituted coloring matters with analkylating agent, or an aralkylating agent, in aqueous suspension, or inan mdlderent solvent, preferably in the presence of an agent capalole-ollining free acid.

ad of employing an yrol the aforementionedSLD'llIIfiGBIlG-l-Q-dlCfiI'bOKYliG acid imid hodies we can make use ofhalogen derivatives thereof, and for the purposes of 7 Ewample l.

" lanedeee nets of th thyl id at ing to the formula CH4: ,4 a

(obtainable by reacting amin on anthracene-l.9-dicarboxylic acidanhydrid) into 17 parts of molten potassium hydrate, while-maintaining atemperature of about 210 C. and continue stirring for some time at thistemperature. take up the melt with water, pass air through the liquiduntil the hydro-compound of the coloring matter has been oxidized andcomplete the precipitation, if necessary, by means of common salt.Filter ofi the coloring matter, wash it with hot water and alcohol anddry it. If desired, it can be still further purified by extraction withboiling glacial acetic acid. It yields a red-brown solution inconcentrated sulfuric acid and from a red-violet vat colors matters canbe obtainedfrom the phenyl-' imid of anthracene-1.9-dicarboxylic acid(obtainable from anilin and anthracene-L9- dicarboxylic acid anhydrid)and from the hydroximid of anthracene (obtainablefrom hydroxylamin andanthracene-l.9-dicarboxylic acid anhydrid).

Example 2.

Place in a reflux apparatus 200 parts of water and 2 parts of thecoloring matter obtainable according to Example 2 of the aforesaidapplication Serial No. 776,541- i. e. by heating 1 part of theanthracene-L9- dicarboxylic acid imid with 5 parts of caustic alkali anda small quantity of water at from 200 to 230 C. until the formation ofthe coloring matter is complete, which coloring matter has been obtamedin a state of fine division by precipitation from a sulfuric acidsolution. Then add 7 parts of potassium carbonate and 10 parts of methyliodid, and boil the'='mixture for 10 hours, and afterwith monomethyl-Then . menace ward filter on and work up. The coloring matter obtainedossesses a tinge of green somewhat more b uish than that of the imtialmaterial, and it is also fast agamst the action of chlorin.

In a similar manner the said initial color.- ing matter can be treatedwith di-methylsulfate, or withthe methyl-ester of toluene sulfonic acidin the presence of caustic alkali, preferably at the temperature of fromExample 5.

Boil together for 3 hours in areflux apparatus, 2 parts of" calcinedsoda, 2 parts of and appears identical with the coloring matterobtainable from the meth 'l-imid of anthracene-Lil-diearboxylic aci asdescribed in the foregoing Example, 1. V v

In this example the nitrobenzene can be replaced by trichlor benzene, ornaphthalene.

Now what we claim is l, The new vatcoloring matters of the anthraeeneseries such as are obtainable by a matter, when dry, is a crystallinepowder melting with caustic alkali anthracene-LQ- dicarboxylic acidimids in which the hydrogen of the imid group is substituted by. aradical, which new coloring matters contain an imid group substituted bya radical, are soluble in alkaline hydrosulfite solution, giving fromred to violet solutions and which dye cotton bluish-eon shades ofexcellent fastness.

\ 2; The new vat coloring matter 'of the anthracene series obtainable bymelting the which shades l/The process of producing vat coloringWitnesses to the signature of Michael matter of the anthracene series bysubject- Kardos:

ing the methyl-imid of anthracene-1.9di- H. QELLINe, carboxylic acid tothe action of a caustic G. VAIDAN. 5 alkaline melt. PAUL NAWIASKY.

In testimony whereof we have hereunto Witnesses to the signature of PaulNawiaset our hands in the presence of two subsky scribing witnesses. J.Anne. LLOYD,

MICHAEL KARDOS. S. S. BERGER.

